CN103619907A - Method for manufacturing biomass-derived polyester and biomass-derived polyester - Google Patents

Method for manufacturing biomass-derived polyester and biomass-derived polyester Download PDF

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Publication number
CN103619907A
CN103619907A CN201280029888.0A CN201280029888A CN103619907A CN 103619907 A CN103619907 A CN 103619907A CN 201280029888 A CN201280029888 A CN 201280029888A CN 103619907 A CN103619907 A CN 103619907A
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biomass
polyester
derived
resource
dicarboxylic acid
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田中阳一郎
森本国弘
大久保拓郎
村田良显
W·M·彼得斯
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Toray Industries Inc
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Provided is a method for manufacturing biomass-derived polyester having excellent dyeability that can greatly reduce the amount of fossil fuels used and suppress increases in carbon dioxide and is not inferior to conventional fossil fuel-derived products with regards to color and thermal stability. The biomass-derived dicarboxylic acid and/or ester-forming derivative thereof used as a raw material satisfies at least one of (A) 0.1 mg KOH/g or less of potassium hydroxide is required to neutralize the acid component extracted by organic solvent per 1 g of dicarboxylic acid and/or ester-forming derivative thereof, (B) 0.05 mg KOH/g or less of potassium hydroxide is required to neutralize the acid component extracted by water per 1 g of dicarboxylic acid and/or ester-forming derivative thereof, and (C) the sulfate ion content is 40 ppm or less.

Description

The manufacture method of the polyester of biomass-derived resource and the polyester of biomass-derived resource
Technical field
The present invention relates to the manufacture method of polyester and the polyester of biomass-derived resource that the raw material by biomass-derived resource obtains.
Background technology
Oil as fossil resource is the important source material on chemical industry, except the worry in the future exhausted, and due to manufacturing process and burn when discarded and discharge a large amount of carbonic acid gas, the environmental problem such as also can cause that global range warms.The use of the material that in this case, reclaimed materials and environmental pressure are little has been subject to gazing at.
To be plant using water and carbonic acid gas by photosynthesis to biomass resource as feedstock conversion, forms, and has starch, carbohydrate, Mierocrystalline cellulose, xylogen etc.Because biomass resource is used carbonic acid gas as raw material in production process, even if use the material of biomass resource to carry out burning disposal and be decomposed into carbonic acid gas and water after use, can not produce new carbonic acid gas yet, owing to according to circumstances can being absorbed by plants again, the renewable resources of being therefore known as.If these biomass resources can be used as the alternative of fossil resource and use, just can suppress the minimizing of fossil resource and the increase of carbonic acid gas.
On the other hand, because the physical strength of polyester, chemical stability, the transparency are excellent, and cheap, be therefore one of synthetic resins of being used by maximum as various fibers, film, sheet material, container etc. of the whole world.People have carried out various research and have attempted by the synthetic large polyester of this usage quantity of reproducible biomass resource.For example reported corn has been fermented, by biotechnology and chemical engineering step, obtain 1, ammediol (1, the ethylene glycol of the polytrimethylene terephthalate that 3-PDO), contains the biomaterial that is derived from non-fossil resource (PPT), biomass-derived resource is as (patent documentations 1～4) such as polyethylene terephthalates (PET) of raw material.But, by these polymkeric substance 14on the bioid rate theory that C concentration is calculated, be respectively 27%(PPT), 20%(PET).On the other hand, although also reported the polybutylene terephthalate that the biological rate of the terephthalic acid composition that uses biomass-derived resource is 94% (patent documentation 5) and polyethylene terephthalate (patent documentation 6), but owing to there being amino acid and the protein that comes from biomass-derived resource in the polyester raw material of biomass-derived resource, the various trace impurities of metallic cation etc., therefore polymerisation reactivity is poor, be difficult to obtain have the polymkeric substance of the viscosity of the degree of being practical stood, enable in addition to obtain, also exist due to the polymkeric substance problems such as significantly painted its purposes is extremely limited.For these problems, the inventor's research group has reported, by making the polyester of biomass-derived resource contain phosphorus compound, can reach polymerisation reactivity good, and can obtain the polyester (patent documentation 7) of the biomass-derived resource of the biological rate of height that polymkeric substance tone is good.But, to compare with the polyester that is derived from fossil resource obtaining by the same terms, tone and thermostability are still poor.For the polyester article by biomass-derived resource replaces the existing polyester article that is derived from fossil resource, require to reach the tone equal with the polyester that is derived from fossil resource in the polyester granulate stage.Particularly for the fiber that will dye etc. and to process, if different from the tone of existing goods in the polyester granulate stage, feel after spinning, dyeing can change with respect to currently available products, therefore requires to reach in particle stage and the existing product that is derived from fossil resource to have equal tone.But the polyester that meets the biomass-derived resource of this requirement does not obtain yet.
Prior art document
Patent documentation
Patent documentation 1: United States Patent (USP) the 6th, 428,767B1(embodiment)
Patent documentation 2: the open CN101046007(claims of Chinese patent)
Patent documentation 3: TOHKEMY 2009-91694 communique (claims)
Patent documentation 4: No. 2009/72462 communique of International Publication (claims)
Patent documentation 5: No. 2010/78328 communique of International Publication (claims)
Patent documentation 6: No. 2009/120457 communique of International Publication (claims)
Patent documentation 7: TOHKEMY 2011-219736 communique (claims)
Summary of the invention
Invent problem to be solved
In order to suppress significantly the minimizing of fossil resource and increasing of carbonic acid gas, the invention provides and can substitute the existing manufacture method of polyester and the polyester of the biomass-derived resource that obtained by the method that is derived from the polyester article of fossil resource and there is the biomass-derived resource of essentially identical tone and thermostability.
The means of dealing with problems
For addressing the above problem, conduct in-depth research, found that, in the manufacture method of polyester of using the dicarboxylic acid of biomass-derived resource and/or the biomass-derived resource of its ester formative derivative, by make to be selected from the content of the dicarboxylic acid of biomass-derived resource and/or the Determination of Organic Acids in its ester formative derivative, mineral acid composition, sulfate ion one of at least in certain limit, just can address the above problem.
That is, the manufacture method of the polyester of biomass-derived resource of the present invention is characterised in that, the dicarboxylic acid of above-mentioned biomass-derived resource and/or its ester formative derivative meet at least one condition in following (A), (B), (C) that is selected from:
(A) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g
(B) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by water is below 0.05mgKOH/g
(C) content of sulfate ion is below 40ppm.
In addition, the manufacture method of the polyester of biomass-derived resource of the present invention is characterised in that, uses dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource that the technique of the operation of following by comprising (1)～(4) obtains.
(1) by fermentation method, by biomass resource, obtained the operation of isopropylcarbinol
(2) by isopropylcarbinol dehydration, obtained the operation of iso-butylene
(3) from iso-butylene, change the operation of p-Xylol into
(4) from p-Xylol, obtain the operation of terephthalic acid and/or its ester formative derivative.
And then the dicarboxylic acid of the biomass-derived resource the present invention relates to and/or its ester formative derivative are characterised in that and meet at least one condition that is selected from above-mentioned (A), (B), (C).In addition, the manufacture method of the dicarboxylic acid of biomass-derived resource of the present invention and/or its ester formative derivative is characterised in that, the dialkyl of the dicarboxylic acid of biomass-derived resource is distilled refining.
Invention effect
Manufacturing method according to the invention, by using dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource that meets at least one condition that is selected from above-mentioned (A), (B), (C) to carry out polymerization, can obtain polymerisation reactivity excellent and have can be practical high viscosity, the polyester of the tone that simultaneously can replace with the polyester article that is derived from fossil resource in the past and the biomass-derived resource of good thermal stability.
The ash content of the dicarboxylic acid of the biomass-derived resource of using in preferred manufacture method of the present invention and/or its ester formative derivative is for below 100ppm.In addition, preferably, with together with the dicarboxylic acid and/or its ester formative derivative of above-mentioned biomass-derived resource, use the glycol of biomass-derived resource as starting material, can further improve biological rate.Also preferably use in addition antioxidant.
The intrinsic viscosity of the polyester of the biomass-derived resource obtaining by manufacture method of the present invention can be 0.4～2.0dlg -1.The tone b value of this polyester can be-10～15 in addition.And the Diethylene Glycol content in this polyester can be 0.1～3.0 % by weight.
The dicarboxylic acid and/or its ester formative derivative that meet the biomass-derived resource one of at least in the above-mentioned condition (A) that is selected from～(C), not only the suitable starting material as manufacturing the polyester of biomass-derived resource, also can be widely used for other purposes.The ash content of the dicarboxylic acid of this biomass-derived resource and/or its ester formative derivative can be for below 100ppm.The dicarboxylic acid of this biomass-derived resource and/or its ester formative derivative can be refined by distillation, preferably by distillation under alkaline condition, are refined and are obtained easily.
Using the polyester of the biomass-derived resource being obtained by the present invention as the substituting of polyester article that is used to now large existing of extensive use and usage quantity and is derived from fossil resource, can significantly suppress the minimizing of fossil resource and the increase of carbonic acid gas.
Working of an invention mode
The manufacture method of the polyester of biomass-derived resource of the present invention must be used the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative as dicarboxylic acid composition.By using the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative as dicarboxylic acid composition, can reaching, improve biological rate, the usage quantity that suppresses fossil resource and the object that carbonic acid gas increases.With respect to whole dicarboxylic acid compositions, the ratio of the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative is preferably more than 80 % by mole, more preferably 100 % by mole.
But, for the synthesis of having the amino acid of biomass-derived resource and alkali composition that protein brings in the dicarboxylic acid of biomass-derived resource and/or the raw material of its ester formative derivative and thering is the trace impurities such as metallic cation of lewis acidity.Therefore with regard to the same method of the Compound Phase with being derived from fossil resource, the reactivity causing due to these impurity is low, can not obtain dicarboxylic acid and/or its ester formative derivative of biomass-derived resource, compare with equal the synthetic of the compound that is derived from fossil resource, the reagent such as catalyzer are essential superfluous, middle operation will be used a large amount of mineral acids, the operation that is obtained dialkyl by dicarboxylic acid must repeat 2 times, in the dicarboxylic acid of the biomass-derived resource consequently obtaining and/or its ester formative derivative except the organic acid and the organic acid as the complete material of unreacted of biomass-derived resource, the mineral acid composition and the sulfate ion that in the middle of also containing in a large number, in operation, use.The existence of these Determination of Organic Acids, mineral acid composition and sulfate ion makes to increase as the Diethylene Glycol of by product, except the melting point depression of the polyester that makes to obtain, infringement thermostability, also can cause the tone of polyester to worsen.
The dicarboxylic acid of biomass-derived resource of the present invention and/or its ester formative derivative preferably obtain by the manufacturing process that comprises refining step.As process for purification, can illustration for example, use the method for ion chromatography, except distillation, recrystallization, distillation, to making water, alcohol, carboxylic acid or their mixture carry out partial crystallization and cleaning, filtration, the unit operation arbitrarily such as dry carries out arbitrary combination, repeats if desired enforcement.Utilize this process for purification, can obtain being suitable for dicarboxylic acid and/or its ester formative derivative of biomass-derived resource of the present invention.Wherein to the dialkyl of the dicarboxylic acid of biomass-derived resource distill refine industrial be easy to be preferred, more refining particularly preferably in distilling under alkaline condition, can be refining with high-level efficiency, guarantee high-recovery, can obtain dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource that the content of Determination of Organic Acids and/or mineral acid composition and/or sulfate ion is restricted simultaneously.
In the present invention so-called under alkaline condition refining the referring under the state that alkaline matter coexists of distillation distill.As alkaline matter, have no particular limits, preferably use the inorganic base substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.More preferably use sodium carbonate, salt of wormwood.
In addition, as the amount that alkaline matter is coexisted, have no particular limits, for example, can be set as the amount more than equivalent of the dicarboxylic acid of biomass-derived resource and/or Determination of Organic Acids that its ester formative derivative contains and/or mineral acid composition and/or sulfate ion.
The dicarboxylic acid of biomass-derived resource of the present invention and/or its ester formative derivative are characterised in that and meet at least one condition in following (A), (B), (C) that is selected from.
(A) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g
(B) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by water is below 0.05mgKOH/g
(C) content of sulfate ion is below 40ppm.
In the present invention, the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative must meet above-mentioned be selected from condition (A), (B), (C) more than one, can meet 1,2 or whole 3.Below, to condition (A)～(C) describe.
In the present invention, the needed potassium hydroxide amount of sour composition that preferably (A) neutralization extracts from the dicarboxylic acid of each gram of biomass-derived resource and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g.If this neutralizes needed potassium hydroxide amount more than 0.1mgKOH/g, polymerisation reactivity is poor, can cause in addition the poor heat stability of the polyester obtaining and painted.In addition, although it is more few better to neutralize needed potassium hydroxide amount, but while reaching lower than 0.0001mgKOH/g, refining step needs too high cost, therefore be unpractical, and if have a small amount of sour composition remaining, particularly when polyethylene terephthalate polymerization, the Diethylene Glycol of by-product only increases a little, tone and the thermostability that can't damage the polyester obtaining, the dyeability of the fiber obtaining is good.Be preferably 0.0001～0.1mgKOH/g, more preferably in the scope of 0.0005～0.08mgKOH/g, in the scope of particularly preferred 0.001～0.05mgKOH/g.
As the organic solvent using in condition of the present invention (A), as long as can will extract as the dicarboxylic acid mono alkyl ester body of impurity and the Determination of Organic Acids such as amino acid of biomass-derived resource in the ester formative derivative of the dicarboxylic acid as biomass-derived resource, it can be any organic solvent, for example can enumerate, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, ethylene glycol, 1, the alcohol such as ammediol, BDO series solvent; The aromatic hydrocarbons series solvents such as benzene, toluene, o-Xylol, p-Xylol, m-xylene; The ether series solvents such as diethyl ether, dibutyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, other also has vinyl acetic monomer, acetonitrile, acetone, dimethyl formamide, dimethyl sulfoxide (DMSO) etc.These solvents can be used separately, and also two or more kinds may be used.Wherein particularly preferably the 1:2 mixture of ethanol and p-Xylol is used as organic solvent.
In the present invention, the needed potassium hydroxide amount of sour composition that preferably (B) neutralization extracts from the dicarboxylic acid of each gram of biomass-derived resource and/or its ester formative derivative by water is below 0.05mgKOH/g.If this neutralizes needed potassium hydroxide amount more than 0.05mgKOH/g, the tone of the polyester obtaining and poor heat stability.In addition, although it is more few better to neutralize needed potassium hydroxide amount, but while reaching lower than 0.0001mgKOH/g, refining step needs too high cost, therefore be unpractical, and if have a small amount of sour composition remaining, particularly when polyethylene terephthalate polymerization, the Diethylene Glycol of by-product only increases a little, tone and the thermostability that can't damage the polyester obtaining, the dyeability of the fiber obtaining is good.Be preferably 0.0001～0.05mgKOH/g, more preferably in the scope of 0.0005～0.015mgKOH/g.
Condition of the present invention (B) is as long as the middle water using can extract the mineral acid composition as impurity in the dicarboxylic acid as biomass-derived resource and/or its ester formative derivative, can be water arbitrarily, for example can enumerate tap water, distilled water, ion exchanged water, ultrapure water etc.In order to improve analysis precision, be preferably distilled water, ion exchanged water or ultrapure water.
Also have, as the sour composition containing in the dicarboxylic acid of biomass-derived resource of the present invention and/or its ester formative derivative, there are Determination of Organic Acids as above and mineral acid composition, substantially with organic solvent, carry out extracter acid composition, water extracts mineral acid composition, also different for neutralizing the needed potassium hydroxide amount of these sour compositions.That is be, indirectly and quantitatively to represent the index of bright foreign matter content separately.Specifically, as Determination of Organic Acids, can be set forth in use biomass-derived resource amino acid and the dialkyl of dicarboxylic acid during as raw material as the dicarboxylic acid mono alkyl ester of the complete material of unreacted etc.The organic acid that these hydrophobicitys are high can not extract out with above-mentioned water substantially, only has the organic solvent extraction of using.On the other hand, as mineral acid composition, except biomass-derived resource mineral acid composition, can also enumerate the mineral acid composition such as usufructuary neutralizing agent, additive, catalyzer in refining, building-up process, such as sulfuric acid, Hydrogen bromide, hydrochloric acid etc., the mineral acid that these wetting abilities are high is substantially gone up and can not with above-mentioned organic solvent extraction out, can only be extracted by water.
In the present invention, (C) the sulfate ion content in the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative is preferably below 40ppm.If this sulfate ion surpasses 40ppm, the tone of the polyester obtaining and thermostability worsen.In addition, although sulfate ion is more few better, but while making it be less than 0.01ppm, refining step needs too high cost, therefore be unpractical, and due to a small amount of existence of sulfate ion, particularly when polyethylene terephthalate polymerization, the Diethylene Glycol of by-product only increase a little, tone and the thermostability that can't damage the polyester obtaining, the dyeability of the fiber obtaining is good.As the content of sulfate ion, preferably in the scope of 0.01～40ppm, more preferably in the scope of 0.01～10ppm.
Dicarboxylic acid and/or its ester formative derivative for biomass-derived resource of the present invention, if the ash content obtaining by aftermentioned method is below 100ppm, just can suppress the painted of polyester, also can suppress in addition the generation of foreign matter, is therefore preferred.Although this ash content is more few better, while making it be less than 0.01ppm, refining step needs too high cost, is therefore unpractical.Be preferably 0.01～100ppm, more preferably in the scope of 0.1～80ppm, in the scope particularly preferably in 0.5～50ppm.In this manual, ash content obtains by the following method, in platinum ware, essence claims dicarboxylic acid and/or its ester formative derivative (W1), with electricradiator, make its burning, add again sulfuric acid make its burning after, with the electric furnaces of 550 ℃, carry out ashing, after the ashing of essence title, the weight (W2) of residue, obtains ash content with following formula.
Ash content (ppm)=(W2/W1) * 10 6
W1: the sample weight (g) that essence claims in platinum ware
W2: the weight of residue (g)
As dicarboxylic acid and/or its ester formative derivative of biomass-derived resource of the present invention, can enumerate the aliphatic dicarboxylic acids such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid; The aromatic dicarboxylic acids such as phthalic acid and/or its ester formative derivative are particularly preferably wherein terephthalic acid and/or its ester formative derivative.As terephthalic acid and/or its ester formative derivative, particularly preferred form can be enumerated, dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid dipropyl, dibutyl terephthalate, terephthalic acid methyl esters (2-hydroxyl second) ester, terephthalic acid two (2-hydroxyl second) ester etc.These materials can be used separately, and also two or more kinds may be used.Dimethyl terephthalate (DMT) if particularly, can distill refiningly, reaches high purity, is therefore preferred.
In the present invention, during the dialkyl of the dicarboxylic acid that the dicarboxylic acid of biomass-derived resource and/or its ester formative derivative are biomass-derived resources, the content of dicarboxylic acid mono alkyl ester is preferably below 0.05 % by weight.If the content of dicarboxylic acid mono alkyl ester is more than 0.05 % by weight, the transesterification reaction of the dialkyl of dicarboxylic acid is low.
Method as obtaining dicarboxylic acid and/or its ester formative derivative of biomass-derived resource of the present invention, has no particular limits, and can use any method.The terephthalic acid of biomass-derived resource, can enumerate such as method of recording in patent documentation 5 and No. 2010/148070 communique of International Publication etc.In addition, can enumerate method of recording in patent documentation 6 and TOHKEMY 2007-176873 communique, No. 2009/64515 communique of International Publication, No. 2009/79213 communique of International Publication, No. 2010/151346 communique of International Publication, TOHKEMY 2011-168501 communique etc.In addition, can also enumerate the method for with alcohol such as methyl alcohol and ethanol, the dicarboxylic acid of the biomass-derived resource being obtained by aforesaid method being carried out to esterification and obtaining etc.Wherein particularly preferably according to No. 2009/79213 communique of International Publication, the p-Xylol of the biomass-derived resource that the technique of the operation of use comprises following (1)～(3) obtains, obtains the method for dicarboxylic acid and/or its ester formative derivative of biomass-derived resource by the technique of following (4).
(1) by fermentation method, by biomass resource, obtained the operation of isopropylcarbinol
(2) by isopropylcarbinol dehydration, obtained the operation of iso-butylene
(3) from iso-butylene, change the operation of p-Xylol into
(4) from p-Xylol, obtain the operation of terephthalic acid and/or its ester formative derivative.
The diol component using in manufacture method as the polyester of biomass-derived resource of the present invention, if the glycol of biomass-derived resource, can reach and improve biological rate, the inhibition usage quantity of fossil resource and the object increasing of carbonic acid gas, be therefore preferred.With respect to whole diol components, the ratio of the glycol of biomass-derived resource more preferably more than 80 % by mole, most preferably is 100 % by mole.
For glycol, good from the viewpoint of the physical property of the polyester that obtains, be preferably selected from least a kind in ethylene glycol, 1,3-PD and BDO.Ethylene glycol if particularly, the fusing point of the polymkeric substance obtaining is high, is therefore preferred.
The method that is obtained these glycol by biomass resource has no particular limits, and can use any method, can enumerate following the whole bag of tricks as an example.
As obtained the method for ethylene glycol by biomass resource, such as the method having by the biomass resource acquisitions such as cane of corn, sugarcane, wheat or farm crop.Have first these biomass resources are converted into starch, water and enzyme are converted into glucose by starch, then by hydrogenation, be converted into Sorbitol Powder, Sorbitol Powder is then under certain temperature and pressure and under the existence of catalyzer, by hydrogenation, form the mixture of various glycol, it is refined and obtains the method for ethylene glycol.As other method, having by biological treatment process is that crop etc. obtains after bio-ethanol by carbohydrate such as sugarcanes, changes ethene into, then through oxyethane, obtains the method for ethylene glycol.As other method further, have by biomass resource and obtain after glycerine, through oxyethane, obtain the method for ethylene glycol.The ethylene glycol obtaining in this way contains various impurity, but preferably as 1 of impurity, 2-propylene glycol, 1,2-butyleneglycol, 2,3-butanediol, BDO are respectively below 1 % by weight, from the physical property of the polyester that obtains, consider, more preferably below 0.5 % by weight, from the tone of the polyester that obtains, consider, more preferably below 0.1 % by weight.
As obtained the method for 1,3-PD by biomass resource, have no particular limits, can be by such as by sugar-fermentings such as glucose, then refine and obtain.
As biomass resource, obtain 1, the method of 4-butyleneglycol, have no particular limits, such as the succsinic acid that can be obtained by fermentation method, succinyl oxide, succinate, toxilic acid, maleic anhydride, maleic acid ester, tetrahydrofuran (THF), gamma-butyrolactone etc., by reduction, wait chemosynthesis to obtain BDO.
In manufacture method of the present invention, can substantially not damage in the scope of effect of the present invention, contain copolymer composition.As copolymer composition, can illustration for example m-phthalic acid, m-phthalic acid-5-sulfonate, phthalic acid, naphthalene-2, aromatic dicarboxylic acid and the ester formative derivatives thereof such as 6-dioctyl phthalate, biphenyl dicarboxylic acid; Succsinic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1,9-nonane diacid, 1, the dicarboxylic acid compositions such as the aliphatic dicarboxylic acids such as 12-dodecanedioic acid and ester formative derivative thereof; The polyoxyethylene glycol that propylene glycol, butyleneglycol, pentanediol, hexylene glycol, molecular weight are 500～20000, Diethylene Glycol, 2-methyl isophthalic acid, ammediol, polyoxygenated tetramethylene glycol, polyoxygenated trimethylene, dihydroxyphenyl propane-ethylene oxide adduct, the such diol component of tetramethylcyclobutanediol.Two or more use alone or in combination of these copolymer compositions.
Most preferred scheme of the present invention is to use the terephthalic acid of biomass-derived resource and/or the dimethyl terephthalate (DMT) of biomass-derived resource as dicarboxylic acid composition, uses the ethylene glycol of biomass-derived resource as the manufacture method of the polyethylene terephthalate of the biomass-derived resource of diol component.
If the biological rate of the polyester of the biomass-derived resource being obtained by the present invention of obtaining by aftermentioned method is more than 60%, can suppress the minimizing of fossil resource and increasing of carbonic acid gas, be therefore preferred.In the present invention, so-called biological rate refers to the D6866 based on ASTM, with respect to the whole carbon atoms in polymkeric substance, with the radiocarbon C14 in the cyclic carbon of nineteen fifty ( 14c) concentration is the ratio of the carbon of the biomass-derived resource obtained of benchmark.Biological rate more preferably more than 70%, is particularly preferably more than 90%, while there is no copolymer composition, most preferably is 100%.
The manufacture method of the polyester of biomass-derived resource of the present invention preferably makes the dicarboxylic acid of (1) glycol and biomass-derived resource carry out esterification, or make the ester formative derivative of the dicarboxylic acid of (2) glycol and biomass-derived resource carry out transesterification reaction, thereby obtain oligopolymer, then decompression in reactor is carried out to polyreaction, thereby obtain the manufacture method of high molecular weight polyesters.
In the manufacture method of the polyester of biomass-derived resource of the present invention, as the catalyzer using in esterification, can use the compound of lithium, magnesium, manganese, calcium, cobalt, zinc, titanium etc., or also can catalyst-free.In addition, as the catalyzer using in transesterification reaction, can use the compound of lithium, magnesium, manganese, calcium, cobalt, zinc, titanium etc. etc.In addition, as the catalyzer using in polyreaction, can use the compound of antimony, titanium, aluminium, tin, germanium etc. etc.
As antimony compounds, can enumerate oxide compound, Antimony Carboxylates, alkoxide antimony of antimony etc., specifically, oxide compound as antimony, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide etc. can be enumerated, as Antimony Carboxylates, antimony acetate, antimony oxalate, antimonypotassium tartrate etc. can be enumerated, as alkoxide antimony, can enumerate three positive fourth weisspiessglanzs, three ethoxyquin antimony etc.
As titanium compound, can enumerate titanium oxide that the hydrolysis of the alkyl dioxides such as titanium complex, titanium isopropylate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, alkyl dioxide obtains, titanium acetylacetone etc.If the titanium complex as sequestrant by polycarboxylic acid and/or hydroxycarboxylic acid and/or polyvalent alcohol wherein, few from the viewpoint of thermostability, tone and the nozzle of polymkeric substance stores is around preferred.As the sequestrant of titanium compound, can enumerate lactic acid, citric acid, mannitol, tripentaerythritol etc.
As aluminum compound, can enumerate ALUMINUM CARBOXYLIC, aluminum alkoxide, aluminium chelate compound, alkaline aluminum compound etc., can enumerate specifically Burow Solution, aluminium hydroxide, aluminium carbonate, ethoxyquin aluminium, AIP, aluminium acetylacetonate, alkaline Burow Solution etc.
As tin compound, can enumerate Mono-n-butyltin, Dibutyltin oxide, aminomethyl phenyl stannic oxide, tetraethyl-stannic oxide, oxidation triethyltin, triethylphosphine hydroxide, monobutyl hydroxyl oxidize tin, monobutyl-tin-trichloride, dibutyltin sulfide etc.
As germanium compound, can enumerate oxide compound, alkoxide germanium of germanium etc., specifically, as the oxide compound of germanium, can enumerate germanium dioxide, four germanium oxides, as alkoxide germanium, can enumerate tetrem germanium oxide, four fourth germanium oxides etc.
As lithium compound, specifically, can enumerate Lithium Oxide 98min, lithium hydroxide, alkoxide lithium, Lithium Acetate, Quilonum Retard etc.
As magnesium compound, specifically, can enumerate magnesium oxide, magnesium hydroxide, alkoxide magnesium, magnesium acetate, magnesiumcarbonate etc.
As manganic compound, specifically, can enumerate Manganous chloride tetrahydrate, Manganese dibromide, manganous nitrate, manganous carbonate, manganese acetylacetonate, manganese acetate etc.
As calcium cpd, specifically, can enumerate calcium oxide, calcium hydroxide, alkoxide calcium, calcium acetate, calcium carbonate etc.
As cobalt compound, specifically, can enumerate cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous carbonate, acetylacetone cobalt, cobalt naphthenate, Cobaltous diacetate tetrahydrate etc.
As zn cpds, specifically, can enumerate zinc oxide, alkoxide zinc, zinc acetate etc.
The manufacture method of the polyester of biomass-derived resource of the present invention is preferably added antioxidant.Due in the polyester raw material of biomass-derived resource, various trace impurities headed by the alkali composition that existence brings with amino acid and the protein of biomass-derived resource, therefore may under the such hot conditions of polyreaction, form foreign matter, make the thermostability of the polyester that obtains worsen and cause painted.By adding antioxidant, the formation that can resist foreign matter, obtains the polyester of the biomass-derived resource of thermostability, polymkeric substance tone excellence.
As antioxidant, have no particular limits, can enumerate phosphorus system, hindered phenol system, sulphur system, hydrazine system, triazole is antioxidant etc.These materials can be used separately or use two or more simultaneously.
As phosphorous antioxidant, bi-ester of phosphite, phosphate compound, phosphinate compound, phosphonate compound, phosphinous acid ester cpds, phosphinate compounds.Wherein, phosphoric acid, trimethyl phosphite 99, triethyl phosphate, diethyl phosphono vinyl acetic monomer etc. suppress the effective of foreign particle generation, make shaping processability good, are therefore preferred.In addition, by two (2 of chemical formula (1) expression, 6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites (PEP-36: rising sun electrification society system), by four (2 of chemical formula (2) expression, 4-di-t-butyl-5-aminomethyl phenyl) ［ 1, 1-biphenyl ］-4, 4 '-bis-base biphosphinates (GSY-P101: large rugged industrial society system), by two (2 of chemical formula (3) expression, 4-di-tert-butyl-phenyl) tetramethylolmethane-diphosphites (PEP-24G: rising sun electrification society's system or IRGAFOS126:CIBA JAPAN company system), by four (2 of chemical formula (4) expression, 4-di-tert-butyl-phenyl) ［ 1, 1-biphenyl ］-4, the phosphorus compounds such as 4 '-bis-base biphosphinates (Zhi Huo SandostabP-EPQ:CLARIANT company of IRGAFOSP-EPQ:CIBA JAPAN company system) are preferred for improving tone and thermostability aspect.These phosphorus compound can be used separately, also can use two or more simultaneously.
Figure BDA0000439952420000141
As hindered phenol, it is antioxidant, can enumerate tetramethylolmethane four ［ 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester ］, the two ［ 3-(3 of sulphur diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester ］, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, 4, two (octyl group the thiomethyl)-O-cresols of 6-etc.Wherein, tetramethylolmethane four ［ 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester ］ (IRGANOX1010:CIBA JAPAN company system) suppresses painted effective, is therefore preferred.
As sulphur, be antioxidant, can enumerate Tyox B, thio-2 acid double tridecyl ester, thio-2 acid two myristins, distearylthiodi-propionate, tetramethylolmethane-tetra-(3-lauryl thiopropionate), tetramethylolmethane-tetra-(3-dodecyl thiopropionate) etc.Tetramethylolmethane-tetra-(3-lauryl thiopropionate) (SumilizeTP-D: Sumitomo Chemical society system) can improve thermostability, resist painted effectively, be therefore preferred wherein.
As hydrazine, be antioxidant, can enumerate decamethylene dicarboxylic acid-bis-(N '-salicyloyl hydrazides), m-phthalic acid two (2-phenoxy group propionyl hydrazides), N-formyl radical-N '-salicyloyl hydrazine etc.
As triazole, be antioxidant, can enumerate benzotriazole, 3-(N-salicyloyl) amino-1,2,4-triazole etc.
In the manufacture method of the polyester of biomass-derived resource of the present invention, the addition of antioxidant has no particular limits, preferably with respect to the polyester obtaining in the scope of 0.1～10000ppm.If addition, in above-mentioned scope, can resist the generation of foreign matter, therefore can obtain forming process good, and the polyester of tone, excellent heat stability.More preferably in the scope of 1～1000ppm, in the scope particularly preferably in 5～500ppm.
For the polyester of the biomass-derived resource being obtained by the present invention, the intrinsic viscosity obtaining by aftermentioned measuring method (［ η ］) is preferably 0.4～2.0dlg -1.The intrinsic viscosity of polyester is the value of measuring at 25 ℃ as solvent with ortho chloro phenol herein, means the index of the mechanical characteristics of polyester.If intrinsic viscosity deficiency 0.4dlg -1, mechanical characteristics is not enough, is difficult to obtain tolerating practical molding.When polyester of the present invention is polyethylene terephthalate, intrinsic viscosity is 0.4～1.5dlg more preferably -1, be particularly preferably 0.6～1.3dlg -1.In addition, when polyester of the present invention is polytrimethylene terephthalate, intrinsic viscosity is 0.6～2.0dlg more preferably -1, be particularly preferably 0.7～1.6dlg -1.When polyester of the present invention is polybutylene terephthalate, intrinsic viscosity is 0.6～2.0dlg more preferably -1, be particularly preferably 0.8～1.8dlg -1.
For the polyester of the biomass-derived resource being obtained by the present invention, the tone while being shred after granulating in-10～15 scope, is preferred from the viewpoint of the tone of the products formeds such as fiber and film by Hunter value b value.The b value more preferably-5～15, more preferably-3～12 of polyester, is particularly preferably 0～10 scope.Hunter value (L, a, b value) is that the colour system based on recording in JIS Z8730 is measured.If generate the content of Determination of Organic Acids in derivative, mineral acid composition, sulfate ion as the dicarboxylic acid of the biomass-derived resource of raw material and/or its ester shape many, b value has the tendency uprising.
In addition, that obtain be preferably below 1.5 with the aberration Δ E of the equal polyester that is derived from fossil resource by aftermentioned method, 1.0 with next essence indifference on visual if, is therefore preferred.The so-called equal polyester that is derived from fossil resource refers under the identical condition of the polyester with biomass-derived resource and carries out esterification or transesterify herein, aggregate under the same conditions by being derived from the glycol of fossil resource and being derived from the polyester that is derived from fossil resource that the dicarboxylic acid of fossil resource forms.
The manufacture method of the polyester of biomass-derived resource of the present invention can be used tone conditioning agent.As mentioned above, although contained impurity may cause that polyester is painted in the polyester raw material of biomass-derived resource, if use tone conditioning agent, just can form good tone.As tone conditioning agent, although have no particular limits for dyestuff, face material, from forming process, consider preferably to use dyestuff.If particularly specifically enumerate by COLOR INDEX GENERIC NAME, can enumerate the Yellow Red tone conditioning agents such as red colour system tone conditioning agent, SOLVENT ORANGE60 such as violet tone conditioning agent, SOLVENT RED24, SOLVENT RED25 such as blue series tone conditioning agent, SOLVENT VIOLET36, SOLVENT VIOLET8 such as SOLVENT BLUE104, SOLVENT BLUE45.Wherein, the violet tone conditioning agents such as the tone conditioning agent of the blue series such as SOLVENT BLUE104 and SOLVENT BLUE45, SOLVENT VIOLET36 are containing easily causing the halogen of corrosion of equipment, thermostability under high temperature is relatively good, color emissivity is excellent, is therefore preferred.These materials can be used separately, also can combine two or more use.The amount of the tone conditioning agent adding has no particular limits, if be aggregated in respect to the polyester obtaining in the scope of 0.1～100ppm, can obtain the polyester that luminance brightness is high, is therefore preferred.More preferably in the scope of 0.5～20ppm, in the scope particularly preferably in 1～5ppm.
The carboxyl end group concentration of the polyester of the biomass-derived resource being obtained by the present invention is preferably in the scope of 1～50 equivalent/ton.Carboxyl end group concentration is lower, and thermostability is better, and in the time of can alleviating melting again, polymkeric substance is painted, and the stores around of the nozzle while reducing melt-spinning, improves stability of spinning process, is therefore preferred.Carboxyl end group concentration is preferably 40 equivalents/below ton.
The thermostability of the polyester of the biomass-derived resource being obtained by the present invention uses " the Δ b value 290 " and " Δ carboxyl end group 290 " that by aftermentioned method, obtain to represent, preferably " Δ b value 290 " is below 2, and preferred " Δ carboxyl end group 290 " is 10 equivalents/below ton.As " Δ b value 290 " herein, be by polyester drying under reduced pressure after 12 hours at 150 ℃, at 290 ℃ of nitrogen atmosphere, heating and melting is 60 minutes, then with aforesaid method, measures b value, using the difference of the b value of heating and melting front and back as Δ b value 290.In addition, as " Δ carboxyl end group 290 ", be by polyester drying under reduced pressure after 12 hours at 150 ℃, at 290 ℃ of nitrogen atmosphere, heating and melting is 60 minutes, then measures carboxyl end group concentration, and the difference of the carboxyl end group concentration before and after heating and melting is as Δ carboxyl end group 290.
For the polyester of the biomass-derived resource being obtained by the present invention, if in the scope of the content of Diethylene Glycol in 0.1～3.0 % by weight, the thermostability of polyester and the color emissivity of trevira are good, are therefore preferred.From the viewpoint of the thermostability of polyester, Diethylene Glycol is more few better, and still, from the viewpoint of the dyeability of trevira, Diethylene Glycol is The more the better.With from being derived from the polyester that the polyester raw material of fossil resource obtains, compare, the content of the Diethylene Glycol of the polyester obtaining from the polyester raw material of biomass-derived resource tends to more, the dyeability of the trevira of biomass-derived resource is good, but poor heat stability sometimes.Therefore as raw material, must use dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource that meets at least one condition in following (A), (B), (C) that is selected to manufacture.
(A) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g
(B) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by water is below 0.05mgKOH/g
(C) content of sulfate ion is below 40ppm.
The content of Diethylene Glycol preferably, in the scope of 0.3～3.0 % by weight, if in the scope of 1.0～2.5 % by weight, is compared tone and thermostability on an equal basis and can improve dyeability with the product that is derived from fossil resource, be therefore particularly preferred.
The manufacture method of the polyester of biomass-derived resource of the present invention, can allocate UV light absorber, fire retardant, fluorescent bleaches, matting agent, softening agent or defoamer or other additives etc. if desired into.The polyester that particularly uses biomass-derived resource during as fiber applications, if add titanium oxide, can be given the preferred luminance brightness of fiber institute and barrier property for dress material, is therefore preferred.
The manufacture method of the polyester of biomass-derived resource of the present invention, in order to obtain the more polyester of high molecular, can carry out solid state polymerization.As solid state polymerization, device, method has no particular limits, can be by under inert atmosphere or carry out heat treated under decompression and implement.Rare gas element, as long as polyester is to inertia, such as enumerating nitrogen, helium, carbonic acid gas etc., but is preferably used nitrogen from economic considerations.In addition, for decompression, preferably making the pressure in device is the condition below 133Pa, and the condition of setting further decompression for can shorten the time that solid-phase polymerization needs, and is therefore favourable.
The polyester of the biomass-derived resource being obtained by the present invention also can recycle.Specifically, use the waste of polyester of biomass-derived resource as raw material, utilize biomass-derived resource or be derived from fossil resource diol component carry out depolymerization reaction, first obtain two (hydroxyalkyl) terephthalate.Can carry out polymerization again to it, but preferably with methyl alcohol, ethanol, carry out transesterify again, form dimethyl terephthalate (DMT) or diethyl terephthalate, by distillation, can be refined into high purity.If use this dimethyl terephthalate ester to carry out polymerization again, polymerisation reactivity is good, can obtain painted few polyester.
The manufacture method of the polyester of biomass-derived resource of the present invention, can produce by any in batchwise polymerization, semi-continuous polymerzation, successive polymerization.
The polyester that the manufacture method of the polyester by biomass-derived resource of the present invention is produced, can adopt common polyester working method to process, and is applicable to forming the molding such as fiber, film, sheet material, bottle and resin, makes various end articles.
The fiber that the polyester of the biomass-derived resource that use is obtained by the present invention forms, can be for dress material purposes, Industrial materials purposes, medical use, but the painted dress material purposes that is preferred for less needing high designability due to polyester, is preferred for Industrial materials purposes because thermostability is high.As Industrial materials purposes, be preferred for fiber for automobile, inner installing materials such as automotive seat, seat harness, ceiling material, the rubber reinforcement fiber of tire.Even if particularly the polyester of biomass-derived resource of the present invention burns and also can suppress increasing of carbonic acid gas, therefore after using, mostly as the mode of heat regeneration, carry out burning disposal, and be preferably used to require the rubber reinforcement fiber of the tire of high thermal stability, for example cord body material, crown material.
The method that is obtained fiber by the polyester of biomass-derived resource of the present invention can adopt common melt-spinning-stretching process.Specifically, polyester granulate being heated to fusing point carries out, after melting, from pore, discharging above, with cooling air, carry out cooling curing, then apply finish, with take off roll, draw, with the take-up mechanism being disposed at after take off roll, batch, thereby can obtain undrawn yarn.For the undrawn yarn batching obtaining like this, with the more than one pair of roller through heating, stretch, finally apply tensioning or lax thermal treatment, thereby form, according to purposes, given the trevira of the physical property such as mechanical characteristic.In addition, in this stretching process, in above-mentioned melt-spinning operation, after traction, not disposablely to batch but carry out continuously, from industrial point of view such as productivitys, consider, it is preferred carrying out continuously elongated.While now applying this stretching-thermal treatment, stretching ratio, draft temperature and heat-treat condition can suitably be selected according to the fiber number of target fibers, intensity, degree of stretching, shrinking percentage etc.
The fiber that the polyester of the biomass-derived resource that use is obtained by the present invention forms, preferred coloring agent specific absorption is more than 90%.Said dyestuff specific absorption is to use spectrophotometer (HITACHI society system herein, U-3000) measure the absorbancy before and after the dyeing of dyestuff body lotion while dyeing by following condition, the value of obtaining by following formula, means the dyeability of trevira, the index of color emissivity.Dyeing condition is as follows.
Dyestuff: Sumikaron Blue S-3RF(A) (azo is dispersed dye, Sumitomo Chemtex company system)
Concentration: 3%owf
Bath raio: 1:20
Dyeing temperature: 110 ℃
Dyeing time: 60 minutes
Dyestuff specific absorption (%)={ (Abs0-Abs1)/Abs0 } * 100
(Abs0: the absorbancy of dyestuff body lotion under maximum extinction wavelength before dyeing, Abs1: the absorbancy of dyestuff body lotion under maximum extinction wavelength after dyeing)
If dyestuff specific absorption is more than 95%, color emissivity, dark color are good, can be described as the fiber of dyeability excellence.More preferably dyestuff specific absorption is more than 90%, to be particularly preferably more than 95%.
Embodiment
The present invention will be described in more detail by the following examples.In addition, the physics value in embodiment is measured as follows.
(1) the needed potassium hydroxide amount of the sour composition (unit: mgKOH/g) that neutralization extracts from dicarboxylic acid and/or its ester formative derivative with organic solvent
Dicarboxylic acid and/or its ester formative derivative 1g are dissolved in the titration solvent being mixed to form by 1:2 by ethanol and p-Xylol, with phenol red and dibromothymolsulfonphthalein, as indicator, also with 0.1mol/L potassium hydroxide-ethanol solution, carry out titration and try to achieve.
(2) the needed potassium hydroxide amount of the sour composition (unit: mgKOH/g) extracting from dicarboxylic acid and/or its ester formative derivative with water in
Dicarboxylic acid and/or its ester formative derivative 1g are added in 30mL ion exchanged water, stir 30 minutes.After stirring, with phenol red and dibromothymolsulfonphthalein, also with 0.1mol/L potassium hydroxide-ethanol solution, carrying out titration tries to achieve.
(3) the sulfate ion content (unit: ppm) in dicarboxylic acid and/or its ester formative derivative
Dicarboxylic acid and/or its ester formative derivative 0.2g are added in 15mL ion exchanged water, stir 30 minutes.After stirring, with syringe strainer, filter dicarboxylic acid and/or its ester formative derivative.Filtrate is provided in chromatography of ions sulfate ion (SO 4 2-) carry out quantitatively, obtaining content.
< ion chromatography condition >
Post: TSK-GEL SUPER IC-AZ(4.6mmI.D. * 15cm)
Leacheate: 2.9mmol/L NaHCO 3/ 3.1mmol/L Na 2cO 3
Detector: conductivity meter
(4) ash content (unit: ppm) of dicarboxylic acid and/or its ester formative derivative
In platinum ware, dicarboxylic acid and/or its ester formative derivative are carried out to essence title, with electricradiator, make its burning, then add sulfuric acid to make its burning, then in the electric furnace of 550 ℃, carry out ashing, essence claims the residue weight after ashing, by following formula, obtains ash content.
Ash content (ppm)=(W2/W1) * 10 6
W1: the sample weight (g) that essence claims in platinum ware
W2: the weight of residue (g)
(5) mensuration (unit: % by weight) of mono alkyl ester content in dicarboxylic acid and/or its ester formative derivative
In 100mL volumetric flask, essence claims dicarboxylic acid and/or its ester formative derivative 0.05g, adds acetonitrile until graticule.After dicarboxylic acid and/or its ester formative derivative are dissolved completely, carry out HPLC analysis.
< HPLC analysis condition >
Post: Inertsil ODS-3(4.6mmID * 250mm, df=5 μ m)
Leacheate: (A liquid) 0.1% phosphate aqueous solution, (B liquid) acetonitrile
Time 0min 20min 25min 30min
B concentration 30 70 30 30
Flow velocity: 1.0mL/min
Column temperature: 40 ℃
Detect wavelength: 240nm
Injection Vol.:2 μ l
(6) intrinsic viscosity of the polyester (dlg of ［η］， unit -1)
With ortho chloro phenol, as solvent, at 25 ℃, measure.
(7) fusing point of polymkeric substance (Tm， unit: ℃)
Use DSC device, first with the heat-up rate of 16 ℃/minute, be warmed up to 280 ℃ from 40 ℃, be incubated 3 minutes and remove thermal history, then by the cooling rate of 16 ℃/minute, cool to 40 ℃, be incubated afterwards 3 minutes.Finally by the heat-up rate of 16 ℃/minute, be warmed up to 280 ℃, using the melting temperature (Tm) obtaining as fusing point (Tm) in the 2nd temperature-rise period.
(8) tone of polymkeric substance
Use colour-difference meter (SUGA trier company system, SM color computer model SM-T45), adopt Hunter value (L, a, the b value) mode of the colour system based on recording in JIS Z8730 to measure the tone of polymkeric substance.
(9) aberration (Δ E)
As the aberration between the polyester that is derived from fossil resource with corresponding (Δ E), if by (the L for tone of the polyester of biomass-derived resource b, a b, b b) represent, by (the L for tone of the equal polyester that is derived from fossil resource p, a p, b p) represent, by following calculating formula, obtain.
ΔE＝｛（L b-L p） 2＋（a b-a p） 2＋（b b-b p） 2｝ 1/2
(10) the carboxyl end group concentration of polymkeric substance (unit: equivalent/ton)
With ortho-cresol, as solvent, use the NaOH aqueous solution of 0.02N at 25 ℃, (Ping Zhao industry society system, COM-550) carries out titration and measures to utilize automatic titration device.
(11) the thermostability index of polymkeric substance (Δ b value 290, Δ carboxyl end group 290)
At 150 ℃, to polyester drying under reduced pressure after 12 hours, at nitrogen atmosphere and 290 ℃, heating and melting is 60 minutes, then with aforesaid method, measures tone and carboxyl end group concentration, and the difference before and after heating and melting is obtained as Δ b value 290, Δ carboxyl end group 290 respectively.
(12) Diethylene Glycol of polymkeric substance (DEG) content (unit: % by weight)
For sample, use monoethanolamine as solvent, 1, under the coexisting of 6-hexylene glycol, heat, then it is cooling to add methyl alcohol to carry out, with after acid neutralization, carry out centrifugation and use gas chromatograph (society of Shimadzu Seisakusho Ltd. system, GC-14A) the Diethylene Glycol content of mensuration supernatant liquor.
(13) phosphorus content (unit: ppm) of polymkeric substance
The sample of shred after heating and melting, is made the formed body with plane on aluminium sheet with press, by fluorescent x-ray Atomic Absorption SpectrophotometerICP, (electric machine industry of science society system, System3270) obtains.
(14) the sulphur atom content (unit: ppm) of polymkeric substance
By sulfate ion reference liquid, (1004mg/L, and the pure pharmaceutical worker of light industry system, Lot.DCQ4971) dilute successively with mark liquid in the phosphoric acid of preparation in addition, makes standardized solution.Wherein, use be suitable for sample concentration analysis standardized solution analytical data production standard curve.
On the other hand, in platinum pot, weigh about 0.1g sample, make it in the incendiary pencil internal combustion of the following analytical equipment of recording, with solution, absorb the gas producing, then a part for absorption liquid is analyzed by ion chromatography.
Analytical equipment: AQF-100, GA-100(Mitsubishi Chemical society system)
Furnace temperature: Inlet; 900 ℃, Outlet; 1000 ℃
Gas: Ar/O 2200mL/ divides
O 2400mL/ divides
Absorption liquid: H 2o 20.1%, interior mark P1 μ g/mL
Absorb liquid measure: 10mL
(15) biological rate measuring method
According to ASTM D6866, obtain biological rate.That is, after sample is pulverized with sand paper and pulverizer, heat together with cupric oxide, complete oxidation is carbonic acid gas, by its with iron powder reducing to graphite, thereby change single carbon compound into.The graphite sample obtaining is imported to AMS device, measure 14c concentration.Also have, also measure oxalic acid (NIST of USS Science and Technology Association provides) as reference material simultaneously 14c concentration.Herein by the ratio of the carbon of sample 14 and carbon 12 ( 14c/ 12c) be designated as 14as, by the ratio of the carbon of reference material 14 and carbon 12 ( 14c/ 12c) be designated as 14ar, obtains Δ by following formula 14c.
Δ 14C＝｛（ 14As- 14Ar）/ 14Ar｝×1000
By following formula from this Δ 14c obtains percent Modern Carbon(pMC).
pMC＝Δ 14C/10＋100
According to the D6866 of American Standard of Testing Materials (ASTM), by being multiplied by 0.93(=100/107.5 shown in following formula on this pMC), thus obtain biological rate.
Biological rate (%)=0.93 * pMC
(16) the dyestuff specific absorption of fiber
(HITACHI society system, U-3000) absorbancy before and after the dyeing of mensuration dyestuff body lotion, obtains dyestuff specific absorption by following formula to use spectrophotometer.
Dyestuff specific absorption (%)={ (Abs0-Abs1)/Abs0 } * 100
(Abs0: the absorbancy of dyestuff body lotion under maximum extinction wavelength before dyeing, Abs1: the absorbancy of dyestuff body lotion under maximum extinction wavelength after dyeing)
Also have, the raw material using in embodiment is as follows.
Production Example 1 < isopropylcarbinol fermentation >
Will be by glucose 85g/L, yeast extract 20g/L, citric acid ferric oxide 20 μ M, H 3bO 35.72mg/L, MnCl 24H 2o3.62mg/L, ZnSO 47H 2o0.444mg/L, Na 2mnO 4h 2o0.78mg/L, CuSO 45H 2o0.158mg/L, CoCl 26H 2o0.0988mg/L, NaHPO 46.0g/L, KH 2pO 43.0g/L, NaCl0.5g/L, NH 4cl2.0g/L, MgSO 40.0444g/L and CaCl 2for example, together with the microorganism storing from refrigerator chamber (colibacillus (Escherichia coli) of proofreading and correct by the mode that the produces isopropylcarbinol) use of the correction M9 substratum of the 40mL volume that 0.00481g/L forms, in the Erlenmeyer flask of 250mL capacity with 0.02～0.05 cultivation OD 600start to cultivate an evening.In the oscillation device of 30 ℃, press 250rpm through approximately 14 hours, starter substratum is grown up.The part of starter substratum moved in the DasGip fermentation unit of 400mL of the correction M9 substratum that has added about 200mL, form approximately 0.1 initial-stage culture OD thereafter 600.Container is arranged in computer control system, the fermentation under monitoring and controlling (by adding suitable alkali) pH6.5, the temperature of 30 ℃, moltenly stays oxygen level and stirring.By the minimum stirring velocity of 200rpm, container is stirred.Air while adopting 12sl/ scatters, and the molten mode of oxygen content of staying of approximately 50% when saturated according to maintenance changes stirring, until OD 600reach till approximately 1.0.Then, with the 1PTG of 0.1mM, container is induced.Through after the continuous growth of approximately 8～10 hours, the airflow during by the minimum stirring velocity of 200rpm and 2.5sl/ reduces and moltenly stays oxygen content until 5% when saturated.In whole experimentation, for oxygen, isopropylcarbinol, ethanol, carbonic acid gas and nitrogen, utilize GC-MS to analyze fermentor vessel waste gas is implemented to METHOD FOR CONTINUOUS DETERMINATION.In whole fermenting process, with sterile manner, from fermentor vessel, take out sample, with it, measure the OD in nutrient solution 600, glucose concn and isopropylcarbinol concentration.It is maximum that isopropylcarbinol reaches about 21.5 hours, and titer is 18g/L, and output is about 70% of maximum theoretical.Nutrient solution is delivered to vacuum distilling, the isobutanol/water mixture of 84:16 is provided, if desired it is again distilled and obtains dry isopropylcarbinol.
Production Example 2 < are derived from the diisobutylene > of isopropylcarbinol
By according to Production Example 1 by the isopropylcarbinol of fermentative production, by distillation separated with fermentation culture.By containing the isopropylcarbinol of 16% water, according to about 10psig and 6hr -1wHSV pass into and be heated to 310 ℃ and added in the chemical reaction equipment of commercially available gamma-alumina catalyst.The water of discharging from the bottom surface of reaction unit, contain the isopropylcarbinol less than 0.1M, to surpass 99% transformation efficiency, collected iso-butylene (gas).Isobutene gas is dried by molecular sieve, is then provided to and remains 140～160 ℃, normal atmosphere, WHSV=1.5hr -1and added in the 2nd reaction unit of ZSM5 catalyzer, the transformation efficiency with approximately 60% obtains comprising the mixture of the triisobutene isomer of approximately 80% diisobutylene isomer and approximately 20% and the resultant of micro-higher molecular weight.
Production Example 3 < are derived from the dimethylbenzene > of diisobutylene
Diisobutylene prepared by the described isopropylcarbinol of recording in Production Example 2, is provided in the reaction unit that has added the η aluminium oxide catalyst adulterating through chromium.Make reaction unit by 1.1hr -1wHSV remain on 550 ℃.Make resultant of reaction condensation, utilize GC-MS to analyze.The output of dimethylbenzene cut is about 20%, and the selectivity with 90% has obtained p-Xylol.
According to the synthetic biomass p-Xylol of Production Example 1～3, be the product of manufacturing based on No. 2009/79213 communique of above-mentioned International Publication, be equivalent to the biomass p-Xylol that Gevo company manufactures.
The terephthalic acid > of the biomass-derived resource of Production Example 4 <
In 1L autoclave, add acetic acid 600g(acetic acid/water=90/10), Cobaltous diacetate (III) tetrahydrate 0.76g, manganese acetate (II) tetrahydrate 0.60g, Hydrogen bromide (hydrogen bromide content 47 % by weight) 0.66mL, with oxygen-nitrogen gas (oxygen content 10 % by weight), be forced into after 0.8MPa, by 1,000rpm, stir on one side and heat in oil bath on one side.When interior temperature reaches 180 ℃, start with the speed of 0.53mL/min to the p-Xylol being obtained by Production Example 3 without interruption in autoclave.In supply p-Xylol, with air, interior pressure is adjusted to after 1.6MPa, according to making extraction flow, be the mode air supply continuously of 2.2mL/min, start the air oxidation reaction of p-Xylol.Regulating the interior temperature making in reaction is on one side 190 ± 5 ℃ of left and right, react 3 hours on one side, leach resultant of reaction, carry out acetic acid cleaning, by 98 % by mole of above yields, obtaining 4-carboxyl benzaldehyde (4-CBA) concentration is the terephthalic acid of the biomass-derived resource below 300ppm.
The dimethyl terephthalate (DMT) > of the biomass-derived resource of comparative example 1-1 <
Terephthalic acid 210g, the methyl alcohol 400g, 98 % by weight sulfuric acid 30mL, copper sulfate (II) the pentahydrate 5.5g that in 1L autoclave, add the biomass-derived resource being obtained by Production Example 4, at 110 ℃, carry out the esterification of 1 hour under 1.5MPa.Leach after resultant of reaction, again by the same terms, carry out esterification.Thereafter, leach resultant of reaction, with methyl alcohol, repeatedly clean, result obtains dimethyl terephthalate (DMT) with the yield of 86 % by mole.Below, sometimes the dimethyl terephthalate (DMT) of biomass-derived resource is designated as to " DMT-b ".
The dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-1 < is distilled > under alkaline condition
For dimethyl terephthalate (DMT) 100 weight parts that obtained by comparative example 1-1, add the sodium carbonate of 0.018 weight part, under 185 ℃, 56hPa, carry out simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is made as 95%.More than sodium carbonate 0.018 weight part is equivalent to the equivalent of needed potassium hydroxide amount (0.19mgKOH/g) in the sour composition of above-mentioned (2) in the dimethyl terephthalate (DMT) that obtained by comparative example 1-1 of neutralization herein, and more than the equivalent of the amount (138ppm) of the sulfate ion being obtained by the mensuration of above-mentioned (3).
The simple distillation > of the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-2 <
Under 185 ℃, 56hPa, the dimethyl terephthalate (DMT) being obtained by comparative example 1-1 is carried out to simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is set as 80%.
The simple distillation > of the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-3 <
Under 185 ℃, 56hPa, the dimethyl terephthalate (DMT) being obtained by comparative example 1-1 is carried out to simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is set as 85%.
The simple distillation > of the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-4 <
Under 185 ℃, 56hPa, the dimethyl terephthalate (DMT) being obtained by comparative example 1-1 is carried out to simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is set as 90%.
The simple distillation > of the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-5 <
Under 185 ℃, 56hPa, the dimethyl terephthalate (DMT) being obtained by comparative example 1-1 is carried out to simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is set as 95%.
The simple distillation > of the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-6 <
Under 185 ℃, 56hPa, the dimethyl terephthalate (DMT) being obtained by comparative example 1-1 is carried out to simple distillation, obtain the dimethyl terephthalate (DMT) of biomass-derived resource.The rate of recovery is set as 99%.
< is derived from the dimethyl terephthalate (DMT) > of fossil resource
Comparative example 1-2
As the dimethyl terephthalate (DMT) that is derived from fossil resource, the dimethyl terephthalate (DMT) of using SK CHEMICAL company to manufacture.Below, sometimes the dimethyl terephthalate (DMT) that is derived from fossil resource is designated as to " DMT-fossil ".
Above, the dimethyl terephthalate (DMT) that relates to embodiment 1-1～embodiment 1-6, comparative example 1-1,1-2, the measurement result of above-mentioned (1)～(5), the needed potassium hydroxide amount of sour composition, (3) sulfate ion content, (4) ash amount and (5) mono alkyl ester content of in the needed potassium hydroxide amount of sour composition that (1) neutralization is taken out with organic solvent extracting, (2), extracting with water are summarized in table 1.
Figure BDA0000439952420000281
The abbreviation symbol using in table 1 as described below.
DMT-b: the dimethyl terephthalate (DMT) of biomass-derived resource
DMT-fossil: the dimethyl terephthalate (DMT) that is derived from fossil resource
The ethylene glycol > of the biomass-derived resource of <
Use India Glycols company preparing ethylene glycol.Below, sometimes the ethylene glycol of biomass-derived resource is designated as to " EG-b ".
< is derived from the ethylene glycol > of fossil resource
Use Japanese catalyzer society preparing ethylene glycol.Below, sometimes the ethylene glycol that is derived from fossil resource is designated as to " EG-fossil ".
The manufacture of < polyethylene terephthalate and evaluation >
Embodiment 2-1
By the dimethyl terephthalate (DMT) of the biomass-derived resource being obtained by embodiment 1-2 (in table, being designated as " DMT-b ") ethylene glycol (India Glycols company system) 60 weight parts of 100 weight parts and biomass-derived resource, the magnesium acetate that is equivalent to 620ppm with respect to the polymkeric substance obtaining are (in table, be designated as " MGA "), in transesterification reactor, under 150 ℃, nitrogen atmosphere, carry out after melting, while stirring, in 4 hours, be warmed up to 240 ℃, methyl alcohol is distillated, carry out transesterification reaction, obtain two (hydroxyethyl) terephthalate.Transferred in polycondensation tank.
After transfer, the ANTIMONY TRIOXIDE SB 203 99.8 PCT that is equivalent to 300ppm in interpolation with respect to the polymkeric substance obtaining (in table, is designated as " Sb 2o 3"), before the trimethyl phosphite 99 (in table; be designated as " TMPA ") that is 200ppm with respect to the polymkeric substance obtaining 30 minutes; in other mixing tank, preliminary election is mixed in the ethylene glycol (India Glycols company system) of biomass-derived resource; stir at normal temperatures after 30 minutes, add its mixture.After 5 minutes, make reaction system decompression start reaction again.Make in reactor to be slowly warmed up to 290 ℃ from 250 ℃, make pressure drop to 40Pa simultaneously.The time that arrives outlet temperature, resulting pressure is all made as 60 minutes.Thereby in the moment that reaches regulation stirring torque, to blasting nitrogen in reaction system, return to normal pressure polycondensation stopped, discharging strand shape and cooling after, cut immediately and obtain polyethylene terephthalate particle.Also having, is 2 hours 20 minutes from decompression beginning to the time that reaches the stirring torque of regulation, and polymerisation reactivity is good.In addition, the tone of the polyethylene terephthalate obtaining, thermostability are all good, have with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-4) polymer property in no way inferior.Polymer property is summarized in table 3.
According to the mode identical with aftermentioned embodiment 2-13, implement again until spinning, dyeing.While evaluating with the fiber obtaining, dyestuff specific absorption is 95%.
Embodiment 2-2
Except using the dimethyl terephthalate (DMT) of the biomass-derived resource being obtained by embodiment 1-6, the mode same by embodiment 2-1 obtains polyethylene terephthalate.Polymerization time, polymer property are summarized in table 3.The needed potassium hydroxide amount of sour composition that neutralization extracts from the dimethyl terephthalate (DMT) of biomass-derived resource with organic solvent, water, sulfate ion content and ash content increase, find thus the delay of polymerization reaction time, painted, the thermostability variation of polymkeric substance tone, and find delay, polymkeric substance painted slightly large of polymerization reaction time.
Embodiment 2-3
Except using citric acid chelating titanium complex (in table, be designated as " citric acid Ti ") replace ANTIMONY TRIOXIDE SB 203 99.8 PCT to convert and be equivalent to beyond 15ppm, by the mode identical with embodiment 2-1, obtain polyethylene terephthalate by titanium atom as polymerizing catalyst and with respect to the polymkeric substance obtaining.Polymerization time, polymer property are summarized in table 3.Polymerisation reactivity is good, and the tone of the polyethylene terephthalate obtaining in addition, thermostability are all good.
Embodiment 2-4
Except the ethylene glycol of biomass-derived resource is changed into, be derived from the ethylene glycol (Japanese catalyzer society system) (in table, being designated as " EG-fossil ") of fossil resource in addition, by the mode identical with embodiment 2-1, obtain polyethylene terephthalate.The characteristic of polymerization time, polyethylene terephthalate is summarized in table 3.Polymerisation reactivity is good, and the tone of the polyethylene terephthalate obtaining in addition, thermostability are all good, but biological rate is low.
Embodiment 2-5～2-8
As substituting of antioxidant phosphorus compound (TMPA), the phosphoric acid (being designated as " PA " in table) of changing into as shown in table 2, phosphorus compound two (2, 6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites (rising sun electrification society system, in table, be designated as " PEP-36 "), phosphorus compound four (2, 4-di-t-butyl-5-aminomethyl phenyl) ［ 1, 1-biphenyl ］-4, 4 '-bis-base biphosphinates (large rugged industrial society system, in table, be designated as " GSY "), hindered phenol based compound tetramethylolmethane four ［ 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester ］ (CIBA JAPAN company system, in table, be designated as " IR1010 "), in addition by the mode identical with embodiment 2-1, obtain polyethylene terephthalate.The characteristic of polymerization time, polyethylene terephthalate is summarized in table 3.Polymerisation reactivity is good, and the tone of the polyethylene terephthalate obtaining in addition, thermostability are all good.
Embodiment 2-9,2-10
Except the addition of phosphorus compound (TMPA) is changed into as shown in table 2, by the mode identical with embodiment 2-1, obtain polyethylene terephthalate.The characteristic of polymerization time, polyethylene terephthalate is summarized in table 3.For the few embodiment 2-9 of the addition of phosphorus compound, thermostability is slightly poor.
Embodiment 2-11
The polymkeric substance obtaining as ethylene glycol (the India Glycols company system) solution of biomass-derived resource during with respect to polymerization adds 2ppm tone conditioning agent, in addition by the mode identical with embodiment 2-1, obtains polyethylene terephthalate.The characteristic of polymerization time, polyethylene terephthalate is summarized in table 3.Polymerisation reactivity is good.
Embodiment 2-12
The polymkeric substance obtaining while carrying out polymerization with respect to ethylene glycol (the India Glycols company system) slurry that makes biomass-derived resource, interpolation is scaled the Titanium particles of 0.3 % by weight by Titanium particles, in addition by the mode identical with embodiment 2-1, obtain polyethylene terephthalate.The characteristic of polymerization time, polyethylene terephthalate is summarized in table 3.Polymerisation reactivity is good, and the tone of the polyethylene terephthalate obtaining in addition, thermostability are all good.
Comparative example 2-1
Except dimethyl terephthalate (DMT) being changed into the dimethyl terephthalate (DMT) of the biomass-derived resource of being synthesized by comparative example 1-1, by the mode identical with embodiment 2-1, obtain polyethylene terephthalate.While using the dimethyl terephthalate (DMT) that neutralizes the needed potassium hydroxide amount of the sour composition biomass-derived resource how of being taken out by organic solvent extracting, polycondensation can not reach target torque, can only obtain the polyethylene terephthalate that viscosity is low.In addition, polymkeric substance tone is significantly colored as yellow, and thermostability is also bad.The characteristic of polyethylene terephthalate is summarized in table 3.
Figure BDA0000439952420000331
In table 2, use abbreviation symbol as follows.
DMT-b: the dimethyl terephthalate (DMT) of biomass-derived resource
EG-b: the ethylene glycol of biomass-derived resource
EG-fossil: the ethylene glycol that is derived from fossil resource
MGA: magnesium acetate
Sb 2o 3: ANTIMONY TRIOXIDE SB 203 99.8 PCT
Citric acid Ti: citric acid chelating titanium complex
TMPA: trimethyl phosphite 99
PA: phosphoric acid
PEP-36: two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites (rising sun electrification society system)
GSY: four (2,4-di-t-butyl-5-aminomethyl phenyl) ［ 1,1-biphenyl ］-4,4 '-bis-base biphosphinates (large rugged industrial society system)
Indigo plant 45:SOLVENT BLUE45(CLARIANT company system)
IR1010: tetramethylolmethane four 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester ］ (IRGANOX1010:CIBA JAPAN company system)
TiO 2: titanium oxide
Figure BDA0000439952420000351
In table 3, use abbreviation symbol as follows.
DEG: Diethylene Glycol
Embodiment 2-13
Ethylene glycol 61 weight parts of the dimethyl terephthalate (DMT) of the biomass-derived resource being obtained by embodiment 1-1 100 weight parts, biomass-derived resource, the magnesium acetate that is equivalent to 250ppm with respect to the polymkeric substance obtaining are carried out after melting in transesterification reactor under 150 ℃, nitrogen atmosphere, while stirring, in 3 hours, be warmed up to 250 ℃, at 250 ℃, keep 1 hour again, carry out transesterification reaction simultaneously, distillate the moment terminated diester permutoid reaction of specified amount methyl alcohol, obtaining the oligopolymer of polyester.Transferred in polyreaction tank.
After transfer, add with respect to the polymkeric substance obtaining, be equivalent to 350ppm ANTIMONY TRIOXIDE SB 203 99.8 PCT, be equivalent to the trimethyl phosphite 99 30 minutes of 200ppm before, in other mixing tank, be pre-mixed in ethylene glycol 0.05 weight part of biomass-derived resource, stir at normal temperatures after 30 minutes, add its mixture.Polyreaction actuator temperature is remained on to 255 ℃, after 5 minutes, make reaction system reduce pressure and start reaction.Make in reactor to be slowly warmed up to 285 ℃ from 255 ℃, simultaneously by pressure decreased to 40Pa.The time that arrives outlet temperature, resulting pressure is all set as from starting polyreaction to 90 minutes.Thereby at the stirring torque that reaches regulation, constantly to reaction system, blast nitrogen and return to normal pressure polyreaction is stopped, from polymerization reactor bottom, with thigh shape, discharge polyester, with after water quench, cut and obtain the polyester granulate of biomass-derived resource.Also have, from reducing pressure, beginning to the time that reaches regulation stirring torque is 164 minutes.In addition, the tone of the polyester of the biomass-derived resource obtaining, thermostability are all good, have with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-2) polymer property in no way inferior.The results are summarized in table 5.
By the vacuum-drying after 12 hours at 150 ℃ of the polyester granulate of the biomass-derived resource obtaining, melting at 285 ℃ of spinning temperatures, then from aperture
Figure BDA0000439952420000361
, 24 of hole counts spinning-nozzle discharge, by circumferential speed, be that the take off roll that 1500m/ divides draw, obtain undrawn yarn.Now, nozzle bore during spinning does not around occur fracture of wire not occurring stores yet substantially.The undrawn yarn obtaining is applied to stretching-thermal treatment with hot-rolling drawing machine under the condition of setting 90 ℃ of draft temperatures, 140 ℃ of thermal treatment temps, 2.2 times of stretching ratios, obtain the drawn yarn of 80dtex-24 monofilament.By the drawn yarn obtaining, make cylinder braid, concise at 95 ℃, at 160 ℃, carry out amorphous intermediate, interpolation Sumikaron Blue S-3RF(A) 3%owf(azo is dispersed dye, Sumitomo Chemtex company system), acetic acid/sodium acetate buffer agent, when the dyeing of carrying out at 110 ℃ by bath raio 1:20 60 minutes is processed, dyestuff specific absorption is 93%, and dyeability is good.
The adjustment > of reference example < mannitol Ti catalyst solution
The there-necked flask of 3L is carried out to nitrogen replacement, add wherein dehydration ethylene glycol (Wako Pure Chemical Industries, Ltd.'s system) 1000mL, mannitol (Tokyo HuaCheng Industry Co., Ltd's system) 5.7g(31.3mmol as reaction solvent), with oil bath, interior temperature is heated to 80 ℃ and stir.With within about 1 hour, making mannitol dissolve, unload and make interior temperature cooling until as 40 ℃ of temperature of reaction oil.When interior temperature is 40 ℃, add titanium tetrabutoxide as titanium compound (Japanese Cao Da society system) 10.6g(31.3mmol), experience thereafter 24 hours reaction times, at 40 ℃ of temperature of reaction, stir.So just obtain water white mannitol Ti catalyst solution (titanium content: 1.5g/L).
Embodiment 2-14
For polymerizing catalyst, by above-mentioned mannitol Ti catalyst solution (in table, be designated as " mannitol Ti ") change into that by titanium atom, to be scaled the addition of 10ppm and trimethyl phosphite 99 (TMPA) as shown in table 4, in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are all good, have with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-3) polymer property in no way inferior.Result and dyeability are summarized in table 5.
Embodiment 2-15,2-16
Using the dimethyl terephthalate (DMT) of changing into respectively the biomass-derived resource being obtained by embodiment 1-2, embodiment 1-3 as shown in table 4 of the dicarboxylic acid composition as raw material, in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are all good, have with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-2) polymer property in no way inferior.Dyeability is excellent in addition.Result is summarized in table 5.
Embodiment 2-17
As substituting of antioxidant trimethyl phosphite 99 (TMPA), with respect to the polymkeric substance that obtains, add the PEP-36(rising sun electrification society system of 500ppm), in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-5) polymer property in no way inferior, and stability of spinning process, dyeability are also good.
Embodiment 2-18
As substituting of antioxidant trimethyl phosphite 99, with respect to the polymkeric substance obtaining, add tetramethylolmethane-tetra-(3-lauryl thiopropionate) (the Sumitomo Chemical society system of 1000ppm, SumilizeTP-D), in addition according to the mode identical with embodiment 2-15, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-6) polymer property in no way inferior, and stability of spinning process, dyeability are also good.In addition, the sulphur atom content in the polyester obtaining is 98ppm.
Embodiment 2-19
As dicarboxylic acid composition, use the dimethyl terephthalate (DMT) (DMT-b) of biomass-derived resource of embodiment 1-2 of 98mol%, the dimethyl ester (SSIA-DM) of the commercially available 5-sodium sulfo isophthalate salt that is derived from fossil resource of 2mol%, in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are with respect to the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-7) polymer property in no way inferior, and stability of spinning process, dyeability are also good.Also have, the sulphur atom content in the polyester obtaining is 2859ppm.
Embodiment 2-20
As dicarboxylic acid composition, use the dimethyl terephthalate (DMT) (DMT-b) of biomass-derived resource of embodiment 1-4 of 98mol%, the dimethyl ester (SSIA-DM) of the commercially available 5-sodium sulfo isophthalate salt that is derived from fossil resource of 2mol%, in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are all slightly poor than the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-7), and stability of spinning process is poor, but dyeability is good.Also have, the sulphur atom content in the polyester obtaining is 2852ppm.
Embodiment 2-21,2-22
In dicarboxylic acid composition, use the dimethyl terephthalate (DMT) of the biomass-derived resource of embodiment 1-4,1-5 as shown in table 4, in addition according to the mode identical with embodiment 2-13, implement the manufacture of polyester of biomass-derived resource and spinning, dyeing.The tone of the polyester of the biomass-derived resource obtaining, thermostability are slightly poorer than the polyester that is derived from fossil resource of manufacturing under the same terms (comparative example 2-2), and stability of spinning process is also poor, but dyeability is good.
Figure BDA0000439952420000401
The abbreviation symbol using in table 4 is as follows.
DMT-b: the dimethyl terephthalate (DMT) of biomass-derived resource
SSIA-DM: the dimethyl ester of 5-sodium sulfo isophthalate salt
EG-b: the ethylene glycol of biomass-derived resource
MGA: magnesium acetate
Sb 2o 3: ANTIMONY TRIOXIDE SB 203 99.8 PCT
Mannitol Ti: mannitol Ti catalyst solution
TMPA: trimethyl phosphite 99
PEP-36: two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites (rising sun electrification society system)
TP-D: tetramethylolmethane-tetra-(3-lauryl thiopropionate), (Sumitomo Chemical society system, SumilizeTP-D)
Figure BDA0000439952420000421
The abbreviation symbol using in table 5 is as follows.
DEG: Diethylene Glycol
Comparative example 2-2
In diol component and dicarboxylic acid composition, use be derived from fossil resource ethylene glycol and dimethyl terephthalate (DMT), in addition according to the mode identical with embodiment 2-13, implement to be derived from the manufacture of polyester of fossil resource and spinning, dyeing.
Comparative example 2-3
In diol component and dicarboxylic acid composition, use be derived from fossil resource ethylene glycol and dimethyl terephthalate (DMT), in addition according to the mode identical with embodiment 2-14, implement to be derived from the manufacture of polyester of fossil resource and spinning, dyeing.
Comparative example 2-4
In diol component and dicarboxylic acid composition, use be derived from fossil resource ethylene glycol and dimethyl terephthalate (DMT), in addition by the mode identical with embodiment 2-1, obtain implementing being derived from the manufacture of polyester of fossil resource and spinning, dyeing.
Comparative example 2-5,2-6
In diol component and dicarboxylic acid composition, use be derived from fossil resource ethylene glycol and dimethyl terephthalate (DMT), in addition according to the mode identical with embodiment 2-17,2-18, implement to be derived from the manufacture of polyester of fossil resource and spinning, dyeing respectively.Also have, the sulphur atom content in the polyester being obtained by comparative example 2-6 is 93ppm.
Comparative example 2-7
In diol component, use be derived from fossil resource ethylene glycol (EG-fossil), in dicarboxylic acid composition, use 98mol% be derived from fossil resource dimethyl terephthalate (DMT) (DMT-fossil), 2mol% commercially available be derived from fossil resource the dimethyl esters (SSIA-DM) of 5-sodium sulfo isophthalate salt, in addition according to the mode identical with embodiment 2-19, implement to be derived from the manufacture of polyester of fossil resource and spinning, dyeing.Also have, the sulphur atom content in the polyester obtaining is 2845ppm.
Above, in comparative example 2-2～2-7 arbitrary example to be stability of spinning process good.Polymer property and chromatic evaluation result are summarized in table 7.
The abbreviation symbol using in table 6 is as follows.
EG-fossil: the ethylene glycol that is derived from fossil resource
DMT-fossil: the dimethyl terephthalate (DMT) that is derived from fossil resource
SSIA-DM: the dimethyl esters of 5-sodium sulfo isophthalate salt
MGA: magnesium acetate
Sb 2o 3: ANTIMONY TRIOXIDE SB 203 99.8 PCT
Mannitol Ti: mannitol Ti catalyst solution
TMPA: trimethyl phosphite 99
PEP-36: two (2,6-di-t-butyl-4-aminomethyl phenyl) tetramethylolmethane-diphosphites (rising sun electrification society system)
TP-D: tetramethylolmethane-tetra-(3-lauryl thiopropionate), (Sumitomo Chemical society system, SumilizeTP-D)
Figure BDA0000439952420000471
The abbreviation symbol using in table 7 is as follows.
DEG: Diethylene Glycol

Claims (11)

1. the manufacture method of the polyester of biomass-derived resource, it is characterized in that using the dicarboxylic acid of biomass-derived resource and/or the polyester that its ester formative derivative is manufactured biomass-derived resource, the dicarboxylic acid of above-mentioned biomass-derived resource and/or its ester formative derivative meet at least one condition in following (A), (B), (C) that is selected from:
(A) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g
(B) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by water is below 0.05mgKOH/g
(C) content of sulfate ion is below 40ppm.
2. the manufacture method of polyester according to claim 1, is characterized in that the dicarboxylic acid of above-mentioned biomass-derived resource and/or the ash content of its ester formative derivative are below 100ppm.
3. the manufacture method of the polyester of biomass-derived resource according to claim 1 and 2, is characterized in that using the glycol of biomass-derived resource.
4. according to the manufacture method of the polyester of the biomass-derived resource described in any one in claim 1～3, it is characterized in that using antioxidant.
5. the manufacture method of the polyester of biomass-derived resource, is characterized in that using dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource that the technique of the operation of following by comprising (1)～(4) obtains,
(1) by fermentation method, by biomass resource, obtained the operation of isopropylcarbinol
(2) by isopropylcarbinol dehydration, obtained the operation of iso-butylene
(3) from iso-butylene, change the operation of p-Xylol into
(4) from p-Xylol, obtain the operation of terephthalic acid and/or its ester formative derivative.
6. the polyester of biomass-derived resource, its polyester that is the biomass-derived resource that obtains by the manufacture method described in any one in claim 1～5, its intrinsic viscosity is 0.4～2.0dlg-1.
7. the polyester of biomass-derived resource, its polyester that is the biomass-derived resource that obtains by the manufacture method described in any one in claim 1～5, its tone b value is-10～15.
8. the polyester of biomass-derived resource, its polyester that is the biomass-derived resource that obtains by the manufacture method described in any one in claim 1～5, its glycol ether content is 0.1～3.0 % by weight.
9. meet dicarboxylic acid and/or its ester formative derivative of the biomass-derived resource of at least one condition in following (A), (B), (C) that is selected from:
(A) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by organic solvent is below 0.1mgKOH/g
(B) the needed potassium hydroxide amount of sour composition that neutralization extracts from each gram of dicarboxylic acid and/or its ester formative derivative by water is below 0.05mgKOH/g
(C) content of sulfate ion is below 40ppm.
10. the dicarboxylic acid of biomass-derived resource according to claim 9 and/or its ester formative derivative, is characterized in that ash content is below 100ppm.
11. manufacture the dicarboxylic acid of biomass-derived resource and/or the method for its ester formative derivative described in claim 9 or 10, it is characterized in that the dialkyl of dicarboxylic acid to distill refining.
CN201280029888.0A 2011-06-17 2012-06-15 Method for manufacturing biomass-derived polyester and biomass-derived polyester Pending CN103619907A (en)

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